US20200030787A1 - Ion-Conducting Membranes - Google Patents
Ion-Conducting Membranes Download PDFInfo
- Publication number
- US20200030787A1 US20200030787A1 US16/552,952 US201916552952A US2020030787A1 US 20200030787 A1 US20200030787 A1 US 20200030787A1 US 201916552952 A US201916552952 A US 201916552952A US 2020030787 A1 US2020030787 A1 US 2020030787A1
- Authority
- US
- United States
- Prior art keywords
- membrane
- vinylbenzyl
- polymer
- styrene
- methylpyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 66
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- -1 cyclic alkyls Chemical group 0.000 claims description 27
- GFYHSKONPJXCDE-UHFFFAOYSA-N 2,3,5-trimethylpyridine Chemical compound CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 claims description 20
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 15
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000446 fuel Substances 0.000 claims description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 12
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 12
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 12
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 12
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 12
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- OXQOBQJCDNLAPO-UHFFFAOYSA-N 2,3-Dimethylpyrazine Chemical compound CC1=NC=CN=C1C OXQOBQJCDNLAPO-UHFFFAOYSA-N 0.000 claims description 8
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 claims description 8
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 claims description 8
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 8
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 8
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 8
- FINHMKGKINIASC-UHFFFAOYSA-N Tetramethylpyrazine Chemical compound CC1=NC(C)=C(C)N=C1C FINHMKGKINIASC-UHFFFAOYSA-N 0.000 claims description 8
- KVFIJIWMDBAGDP-UHFFFAOYSA-N ethylpyrazine Chemical compound CCC1=CN=CC=N1 KVFIJIWMDBAGDP-UHFFFAOYSA-N 0.000 claims description 8
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- IAEGWXHKWJGQAZ-UHFFFAOYSA-N trimethylpyrazine Chemical compound CC1=CN=C(C)C(C)=N1 IAEGWXHKWJGQAZ-UHFFFAOYSA-N 0.000 claims description 8
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 7
- BKFRZOZNMWIFLH-UHFFFAOYSA-N 1-decyl-2-methylimidazole Chemical compound CCCCCCCCCCN1C=CN=C1C BKFRZOZNMWIFLH-UHFFFAOYSA-N 0.000 claims description 7
- GNCJRTJOPHONBZ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1h-imidazole Chemical compound CC1(C)NC=NC1(C)C GNCJRTJOPHONBZ-UHFFFAOYSA-N 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000013626 chemical specie Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- HVOYZOQVDYHUPF-UHFFFAOYSA-N n,n',n'-trimethylethane-1,2-diamine Chemical compound CNCCN(C)C HVOYZOQVDYHUPF-UHFFFAOYSA-N 0.000 claims description 7
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 6
- BJMUOUXGBFNLSN-UHFFFAOYSA-N 1,2-dimethylindole Chemical compound C1=CC=C2N(C)C(C)=CC2=C1 BJMUOUXGBFNLSN-UHFFFAOYSA-N 0.000 claims description 6
- QDVBKXJMLILLLB-UHFFFAOYSA-N 1,4'-bipiperidine Chemical compound C1CCCCN1C1CCNCC1 QDVBKXJMLILLLB-UHFFFAOYSA-N 0.000 claims description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 6
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical compound C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 claims description 6
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 6
- AMSDWLOANMAILF-UHFFFAOYSA-N 2-imidazol-1-ylethanol Chemical compound OCCN1C=CN=C1 AMSDWLOANMAILF-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 6
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 claims description 6
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 claims description 6
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 6
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 6
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 6
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 6
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 6
- WMJMABVHDMRMJA-UHFFFAOYSA-M [Cl-].[Mg+]C1CCCCC1 Chemical compound [Cl-].[Mg+]C1CCCCC1 WMJMABVHDMRMJA-UHFFFAOYSA-M 0.000 claims description 5
- DQDWATOXYCARFV-UHFFFAOYSA-M magnesium;2-methanidylpropane;bromide Chemical compound [Mg+2].[Br-].CC(C)[CH2-] DQDWATOXYCARFV-UHFFFAOYSA-M 0.000 claims description 5
- KGIFNEFQLJMDQJ-UHFFFAOYSA-N 1,2,2,5,5-pentamethylpyrrolidine Chemical compound CN1C(C)(C)CCC1(C)C KGIFNEFQLJMDQJ-UHFFFAOYSA-N 0.000 claims description 4
- XULIXFLCVXWHRF-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidine Chemical compound CN1C(C)(C)CCCC1(C)C XULIXFLCVXWHRF-UHFFFAOYSA-N 0.000 claims description 4
- GZXXANJCCWGCSV-UHFFFAOYSA-N 2,3-Diethylpyrazine Chemical compound CCC1=NC=CN=C1CC GZXXANJCCWGCSV-UHFFFAOYSA-N 0.000 claims description 4
- RNIPJYFZGXJSDD-UHFFFAOYSA-N 2,4,5-triphenyl-1h-imidazole Chemical compound C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 RNIPJYFZGXJSDD-UHFFFAOYSA-N 0.000 claims description 4
- WRXNJTBODVGDRY-UHFFFAOYSA-N 2-pyrrolidin-1-ylethanamine Chemical compound NCCN1CCCC1 WRXNJTBODVGDRY-UHFFFAOYSA-N 0.000 claims description 4
- XYYXDARQOHWBPO-UHFFFAOYSA-N 3,5-dimethyl-1h-1,2,4-triazole Chemical compound CC1=NNC(C)=N1 XYYXDARQOHWBPO-UHFFFAOYSA-N 0.000 claims description 4
- MXDRPNGTQDRKQM-UHFFFAOYSA-N 3-methylpyridazine Chemical compound CC1=CC=CN=N1 MXDRPNGTQDRKQM-UHFFFAOYSA-N 0.000 claims description 4
- IYQKSFDFSHYLNT-UHFFFAOYSA-N 4-methyl-2-pyrrol-1-ylpyridine Chemical compound CC1=CC=NC(N2C=CC=C2)=C1 IYQKSFDFSHYLNT-UHFFFAOYSA-N 0.000 claims description 4
- LVILGAOSPDLNRM-UHFFFAOYSA-N 4-methylpyrimidine Chemical compound CC1=CC=NC=N1 LVILGAOSPDLNRM-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 4
- HJJDFXZAXVAOPK-UHFFFAOYSA-N [Mg]CCC=C Chemical compound [Mg]CCC=C HJJDFXZAXVAOPK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012972 dimethylethanolamine Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 4
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- 239000001569 carbon dioxide Substances 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 12
- 238000010248 power generation Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 229940031098 ethanolamine Drugs 0.000 description 5
- 150000004820 halides Chemical group 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 229960004011 methenamine Drugs 0.000 description 5
- 229960004418 trolamine Drugs 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229940086542 triethylamine Drugs 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- PKDYVBBBBHQJIZ-UHFFFAOYSA-N 1-but-3-enyl-4-ethenylbenzene Chemical compound C=CCCC1=CC=C(C=C)C=C1 PKDYVBBBBHQJIZ-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 3
- 0 [1*]N1C([5*])=C([4*])[N+]([3*])=C1[2*] Chemical compound [1*]N1C([5*])=C([4*])[N+]([3*])=C1[2*] 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- FPDNKWSQWXOPSC-UHFFFAOYSA-N 1-(methylamino)ethanol Chemical compound CNC(C)O FPDNKWSQWXOPSC-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- PYFVEIDRTLBMHG-UHFFFAOYSA-N 2,3-dimethyl-1h-indole Chemical compound C1=CC=C2C(C)=C(C)NC2=C1 PYFVEIDRTLBMHG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 206010034962 Photopsia Diseases 0.000 description 1
- YPJGFXMVFBGFBS-UHFFFAOYSA-M [Cl-].CC1=CC=CC=C1C[Mg+] Chemical compound [Cl-].CC1=CC=CC=C1C[Mg+] YPJGFXMVFBGFBS-UHFFFAOYSA-M 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FKRZJHINSOKNDI-UHFFFAOYSA-M magnesium;1-methanidyl-3-methoxybenzene;chloride Chemical compound [Mg+2].[Cl-].COC1=CC=CC([CH2-])=C1 FKRZJHINSOKNDI-UHFFFAOYSA-M 0.000 description 1
- SWTDOBDFYXFIPN-UHFFFAOYSA-M magnesium;2-ethyl-1,3-dioxane;bromide Chemical compound [Mg+2].[Br-].[CH2-]CC1OCCCO1 SWTDOBDFYXFIPN-UHFFFAOYSA-M 0.000 description 1
- SCEZYJKGDJPHQO-UHFFFAOYSA-M magnesium;methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1 SCEZYJKGDJPHQO-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013580 millipore water Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000065 phosphene Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/28—Polymers of vinyl aromatic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/28—Polymers of vinyl aromatic compounds
- B01D71/281—Polystyrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the field of the invention is electrochemistry.
- the compositions and membranes are useful for the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells, water purification and carbon dioxide capture systems.
- membranes that are useful, if not superior, for the electrolysis of water, batteries, electric power generation using fuel cells, and water purification and carbon dioxide capture systems.
- An anion-conducting membrane comprising a polymer comprising the reaction products of vinylbenzyl-R s , vinylbenzyl-R x and styrene-R t wherein
- the total weight of the styrene-R t is at least 10% of the weight of the polymer.
- vinylbenzyl-R s comprises the reaction product of a benzyl-X, wherein X is a halogen, with at least one of: 1,2,2,6,6-pentamethylpiperidine, 1,2,2,5,5-pentamethylpyrrolidine, tetramethylimidazole, triethylamine, tripropylamine, trimethylamine, N-methylpiperdine, 1-ethylpiperidine, piperidine, 1,4′-bipiperidine, 1-methylpyrrolidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 1-pyrrolidine ethanamine, 2,3,5-trimethylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, 2,4-dimethylpyridine, 2,3,5-trimethylpyridine, 4-methyl-2-(1-pyrrolyl)pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, pyridine, 4,4′-dipyridyl, 2,2
- vinylbenzyl-R x comprises at least one of: (i) benzyl-OH, (ii) benzyl-X, wherein X is a halide, (iii) a benzyl crosslinked to vinylbenzyl-R s , styrene-R t or a different vinylbenzyl-R x , and (iv) the reaction product of a benzyl-X with at least one of: 1,2,2,6,6-pentamethylpiperidine, 1,2,2,5,5-pentamethylpyrrolidine, tetramethylimidazole, triethylamine, tripropylamine, trimethylamine, N-methylpiperdine, 1-ethylpiperidine, piperidine, 1,4′-bipiperidine, 1-methylpyrrolidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 1-pyrrolidine ethanamine, 2,3,5-trimethylpyridine, 2,4,6-
- At least one of R s , and R x are not positively charged cyclic amines, Cl or OH.
- both R s , and R x are not positively charged cyclic amines, Cl or OH.
- R s , R t and R x are each not positively charged cyclic amines, Cl or OH.
- Vinylbenzyl-R x and Styrene-R t are not divinylbenzene.
- R t is a hydrogen or a linear alkyl.
- the polymer will have a molecular weight between 1000 and 10,000,000 atomic units (A.U.) preferably between 10,000 and 1,000,000 A.U., most preferably between 25,000 and 250,000 A.U.
- the polymeric composition is in the form of a membrane.
- the membrane has a preferred thickness of 10-300 micrometers.
- the membrane has an area specific resistance of 0.1 ohm-cm 2 or less.
- any numerical value ranges recited herein include all values from the lower value to the upper value in increments of one unit, provided that there is a separation of at least two units between any lower value and any higher value.
- concentration of a component or value of a process variable such as, for example, size, angle size, pressure, time and the like, is, for example, from 1 to 98, specifically from 20 to 80, more specifically from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, and the like, are expressly enumerated in this specification.
- one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
- polymer electrolyte membrane refers to both cation exchange membranes, which generally comprise polymers having multiple covalently attached negatively charged groups, and anion exchange membranes, which generally comprise polymers having multiple covalently attached positively charged groups.
- Typical cation exchange membranes include proton conducting membranes, such as the perfluorosulfonic acid polymer available under the trade designation NAFION from E. I. du Pont de Nemours and Company (DuPont) of Wilmington, Del.
- anion exchange membrane electrolyzer refers to an electrolyzer with an anion-conducting polymer electrolyte membrane separating the anode from the cathode.
- EMIM 1-ethyl-3-methylimidazolium cations
- CV refers to cyclic voltammetry
- Millipore water is water that is produced by a Millipore filtration system with a resistivity of at least 18.2 megaohm-cm.
- imidazolium refers to a positively charged ligand containing an imidazole group. This includes a bare imidazole or a substituted imidazole.
- R 1 -R 5 are each independently selected from hydrogen, halides linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
- pyridinium refers to a positively charged ligand containing a pyridine group. This includes a bare pyridine or a substituted pyridine.
- R 6 -R 11 are each independently selected from hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
- phosphonium refers to a positively charged ligand containing phosphorous. This includes substituted phosphorous.
- R 12 -R 15 are each independently selected from hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
- positively charged cyclic amine refers to a positively charged ligand containing a cyclic amine. This specifically includes imidazoliums, pyridiniums, pyrazoliums, pyrrolidiniums, pyrroliums, pyrimidiums, piperidiniums, indoliums, triaziniums, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
- R 16 , R 17 and R 18 are each independently selected from hydrogen, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, but not polymers.
- substituted ethene refers to a monomer of the form:
- R 1 -R 4 are each independently selected from hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, including polymers.
- water purification system refers to a device that removes unwanted constituents from water and, in the case of a membrane-based device, one that employs a membrane as a barrier that allows certain substances to pass through while blocking others.
- battery refers to a device that generates electricity via an electrochemical reaction between substances stored internally within the battery.
- fuel cell refers to a device that generates electricity via an electrochemical reaction between substances that are supplied to the fuel cell from an external source.
- electrolyticzer refers to an electrochemical device that uses electrical energy to convert a substance into constituent substances.
- the device uses electricity to convert water into hydrogen and oxygen.
- CO 2 capture system refers to a device that is able to separate CO 2 from a gas or liquid stream.
- the objective of this example is to provide a number of alternate membranes that are useful for the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification.
- Step 1 Inhibitor free styrene was prepared by washing styrene (Sigma Aldrich, Saint Louis, Mo.) with two equal volumes of 7.5% aqueous sodium hydroxide. The inhibitor free styrene was then washed with four equal volumes of water to make sure it was neutralized, and was then dried over anhydrous magnesium sulfate. The tert-butylcatechol (TBC) inhibitor in the vinylbenzyl chloride (VBC) was removed by extraction with 0.5% potassium hydroxide solution until a colorless extract was obtained. This extract was washed with water until neutral and then was dried over anhydrous magnesium sulfate.
- TBC tert-butylcatechol
- VBC vinylbenzyl chloride
- Step 2 Poly(vinylbenzyl chloride-co-styrene) was then synthesized by heating a solution of inhibitor free styrene (Sigma-Aldrich) (10.0581 g, 96.57 mmol) and vinylbenzyl chloride (Sigma-Aldrich) (6.2323 g, 40.84 mmol) in chlorobenzene (Sigma-Aldrich) (15 ml) at 60-65° C. in an oil bath for 12-18 hours under argon gas with AIBN ( ⁇ , ⁇ ′-Azoisobutyronitrile, Sigma-Aldrich) (0.1613 g, 0.99 wt % based on the total monomers weight) as initiator. The copolymer was precipitated in ethanol and dried under vacuum.
- AIBN ⁇ , ⁇ ′-Azoisobutyronitrile, Sigma-Aldrich
- Step 3 The resultant copolymer was dissolved in 1-Methoxy-2-propanol (Sigma Aldrich) to form a solution that was about 30% by weight of polymer.
- Step 4 The solution from step 3 was heated to 60° C., and 1-Decyl-2-methylimidazole was added and the solution was continuously stirred for 48 hours.
- Step 5 Next, an attempt was made to manufacture membranes from each of the solutions prepared in step 4 by casting them directly onto a polyethylene terephthalate (PET) liner.
- PET polyethylene terephthalate
- the thickness of the solution on the PET was controlled by a film applicator (MTI Corporation, Richmond, Calif.) with an adjustable doctor blade.
- the membranes were then dried in a vacuum oven at 80° C. for 300 minutes, and then 120° C. for 200 minutes.
- Membranes were successfully prepared from the following amines: 1,1,3,3-Tetramethylguanidine, 1-Decyl-2-methylimidazole, 1-Ethylpiperidine, 1-methylpyrrolidine, 2,2′-Bipyridyl, 2,3,5-Trimethylpyridine, 2-Methylpyridine, Pyridine, 3-Methylpyridine, 4,4′-dipyridyl, 4-Methylpyridine, N,N,N′,N′-Tetramethyl-1,6-hexanediamine, N,N-Dicyclohexylmethylamine, 1-(2-hydroxyethyl)imidazole, N,N-Dimethylcyclohexylamine, N-methyl Piperdine, Tetramethyl Imidazole, 1-methylimidazole, 1,2-dimethyl imidazole, Tributyl amine, triethyl amine, Trimethyl amine, Triphenyl phosphine, Tripropyl amine.
- NMR Nuclear Magnetic Resonance
- the specific area resistance of the each of the membranes produced in Specific Example 1 was also measured. In all cases the resultant membranes had an area specific resistance below 0.1 ohm-cm 2 in 1 M KOH so that they are useful as ion conductors for at least one of: the electrolysis of water, electrolysis of carbon dioxide, batteries, electric power generation using fuel cells, water purification, and CO 2 capture systems.
- the objective of this example is to show that an anion-conducting membrane comprising a polymer comprising the reaction products of vinylbenzyl-R s , vinylbenzyl-R x and styrene-R t , wherein
- Polymers with heteroaryls can be synthesized using the heteroaryl Grignard reagents disclosed in Barl, et al. (Heterocycles, Vol.
- the specific area resistance the membrane produced in Specific Example 2 was also measured.
- the membrane had an area specific resistance below 0.1 ohm-cm 2 in 1 M KOH so that it may be useful for at least one of: the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification.
- the objective of this example is to show that an anion-conducting membrane comprising a polymer comprising the reaction products of vinylbenzyl-R s , vinylbenzyl-R x and styrene-R t wherein
- the specific area resistance the membrane produced in Specific Example 3 was also measured.
- the membrane had an area specific resistance below 0.1 ohm-cm 2 in 1 M KOH so that it may be useful for at least one of: the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification.
- the objective of this example is to provide additional examples of anion-conducting membranes comprising a polymer comprising the reaction products of vinylbenzyl-R s , vinylbenzyl-R x and styrene-R t wherein
- the specific area resistance of the each of the membranes produced in Specific Example 4 was also measured. In all cases the resultant membranes had an area specific resistance below 0.1 ohm-cm 2 in 1 M KOH so that they are useful for at least one of: the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification.
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Abstract
Description
- The present application is a continuation in part of U.S. patent application Ser. No. 15/810,106 filed on Nov. 12, 2017, entitled “Ion-Conducting Membranes”. The '106 patent is, in turn, a continuation-in-part of U.S. patent application Ser. No. 15/400,775 filed on Jan. 6, 2017 (now U.S. Pat. No. 9,849,450 issued on Dec. 26, 2017), also entitled “Ion-Conducting Membranes”. The '775 application is, in turn, a continuation in part of U.S. patent application Ser. No. 15/090,477 filed on Apr. 4, 2016 (now U.S. Pat. No. 9,580,824 issued on Feb. 28, 2017), also entitled “Ion-Conducting Membranes”. The '477 application is, in turn, a continuation-in-part of U.S. patent application Ser. No. 14/704,935 filed on May 5, 2015, also entitled “Ion-Conducting Membranes” (now U.S. Pat. No. 9,370,773 issued on Jun. 21, 2016). The '935 application was, in turn, a continuation-in-part of International Application No. PCT/US2015/14328, filed on Feb. 3, 2015, entitled “Electrolyzer and Membranes”. The '328 international application claimed priority benefits, in turn, from U.S. provisional patent application Ser. No. 62/066,823, filed on Oct. 21, 2014.
- The '935 application was also a continuation-in-part of International Application No. PCT/US2015/26507 filed on Apr. 17, 2015, entitled “Electrolyzer and Membranes”. The '507 international application also claimed priority benefits, in turn, from U.S. provisional patent application Ser. No. 62/066,823 filed on Oct. 21, 2014.
- The '106 parent application, the '775 application, the '477 application, the '935 application, the '823 provisional application, and the '328 and '507 international applications are each hereby incorporated by reference herein in their entirety.
- This application is also related to U.S. patent application Ser. No. 14/035,935 filed on Sep. 24, 2013, entitled “Devices and Processes for Carbon Dioxide Conversion into Useful Fuels and Chemicals” (now U.S. Pat. No. 9,370,733; U.S. patent application Ser. No. 12/830,338 filed on Jul. 4, 2010, entitled “Novel Catalyst Mixtures”; International application No. PCT/2011/030098 filed Mar. 25, 2011, entitled “Novel Catalyst Mixtures”; U.S. patent application Ser. No. 13/174,365 filed on Jun. 30, 2011, entitled “Novel Catalyst Mixtures”; International application No. PCT/US2011/042809 filed Jul. 1, 2011, entitled “Novel Catalyst Mixtures”; U.S. patent application Ser. No. 13/530,058 filed on Jun. 21, 2012, entitled “Sensors for Carbon Dioxide and Other End Uses”; International application No. PCT/US2012/043651 filed on Jun. 22, 2012, entitled “Low Cost Carbon Dioxide Sensors”; and U.S. patent application Ser. No. 13/445,887 filed on Apr. 12, 2012, entitled “Electrocatalysts for Carbon Dioxide Conversion”.
- The field of the invention is electrochemistry. The compositions and membranes are useful for the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells, water purification and carbon dioxide capture systems.
- U.S. Pat. Nos. 9,370,773, 9,481,939, 9,580,824, 9,815,021, 9,849,450, 9,943,841, 9,945,040, 9,957,624, 9,982,353, 10,047,446, 10,147,974, 10,173,169, and U.S. patent application Ser. Nos. 15/810,106, 15/908,325, 15/922,883, 15/967,293, 16/024,827, 16/164,289, 16/238,425, and 16/429,868 (Masel et al.) disclose a number of ion conducting membranes. These membranes were optimized for carbon dioxide electrolysis.
- Disclosed herein are membranes that are useful, if not superior, for the electrolysis of water, batteries, electric power generation using fuel cells, and water purification and carbon dioxide capture systems.
- An anion-conducting membrane comprising a polymer comprising the reaction products of vinylbenzyl-Rs, vinylbenzyl-Rx and styrene-Rt wherein
- (a) Rs is a positively charged amine group or phosphene
- (b) Rx is independently selected from OH—, halogens, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls or polymers thereof.
- (c) Rt is independently selected from hydrogen, OH—, halogens, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, and heteroalkylaryls.
- (d) Rx is a different chemical species than Rs
- (e) styrene-Rt is a different chemical species than vinylbenzyl-Rs and vinylbenzyl-Rx
- (f) the total weight of the vinylbenzyl-Rs is at least 10% of the weight of the polymer
- (g) the total weight of the vinylbenzyl-Rx is at least 1% of the weight of the polymer
- (h) the total weight of the styrene-Rt is at least 1% of the weight of the polymer.
- In a preferred embodiment the total weight of the styrene-Rt is at least 10% of the weight of the polymer.
- In a preferred embodiment, vinylbenzyl-Rs comprises the reaction product of a benzyl-X, wherein X is a halogen, with at least one of: 1,2,2,6,6-pentamethylpiperidine, 1,2,2,5,5-pentamethylpyrrolidine, tetramethylimidazole, triethylamine, tripropylamine, trimethylamine, N-methylpiperdine, 1-ethylpiperidine, piperidine, 1,4′-bipiperidine, 1-methylpyrrolidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 1-pyrrolidine ethanamine, 2,3,5-trimethylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, 2,4-dimethylpyridine, 2,3,5-trimethylpyridine, 4-methyl-2-(1-pyrrolyl)pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, pyridine, 4,4′-dipyridyl, 2,2′-bipyridyl, tributylamine, N,N-diisopropylethylamine, triphenylamine, N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, triphenylphosphine, 1,2-dimethylindole, indole, 1-methylindole, hexamethylenetetramine, 2,3,5,6-tetramethylpyrazine, 2,3,5-trimethylpyrazine, 2,3-dimethylpyrazine, 3-methylpyridazine, 2-methylpyrazine, 2,3-diethylpyrazine, ethylpyrazine, pyrazine, 1-methylimidazole, pyrimidine, 4-methylpyrimidine, pyridazine, triazole, 3,5-dimethyl-1,2,4-triazole, 1,2-dimethylimidazole, 2,4,5-triphenylimidazole, 1-decyl-2-methylimidazole, 1-(2-hydroxyethyl)imidazole, guanidine, tetramethyl guanidine, dipiperidine, dipyridine, ethylenediamine, propylenediamine, N,N,N′-trimethylethylenediamine, ethylenediaminetetraacetic acid, alkyldiamines, other diamines, ethanolamine, triethanolamine, methylethanolamine, dimethylethanolamine, propanolamine, 3-butenylmagnesium, isobutylmagnesium bromide, cyclohexylmagnesium chloride, and amino acid.
- In a preferred embodiment, vinylbenzyl-Rx comprises at least one of: (i) benzyl-OH, (ii) benzyl-X, wherein X is a halide, (iii) a benzyl crosslinked to vinylbenzyl-Rs, styrene-Rt or a different vinylbenzyl-Rx, and (iv) the reaction product of a benzyl-X with at least one of: 1,2,2,6,6-pentamethylpiperidine, 1,2,2,5,5-pentamethylpyrrolidine, tetramethylimidazole, triethylamine, tripropylamine, trimethylamine, N-methylpiperdine, 1-ethylpiperidine, piperidine, 1,4′-bipiperidine, 1-methylpyrrolidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 1-pyrrolidine ethanamine, 2,3,5-trimethylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, 2,4-dimethylpyridine, 2,3,5-trimethylpyridine, 4-methyl-2-(1-pyrrolyl)pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, pyridine, 4,4′-dipyridyl, 2,2′-bipyridyl, tributylamine, N,N-diisopropylethylamine, triphenylamine, N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, triphenylphosphine, 1,2-dimethylindole, indole, 1-methylindole, hexamethylenetetramine, 2,3,5,6-tetramethylpyrazine, 2,3,5-trimethylpyrazine, 2,3-dimethylpyrazine, 3-methylpyridazine, 2-methylpyrazine, 2,3-diethylpyrazine, ethylpyrazine, pyrazine, 1-methylimidazole, pyrimidine, 4-methylpyrimidine, pyridazine, triazole, 3,5-dimethyl-1,2,4-triazole, 1,2-dimethylimidazole, 2,4,5-triphenylimidazole, 1-decyl-2-methylimidazole, 1-(2-hydroxyethyl)imidazole, guanidine, tetramethyl guanidine, dipiperidine, dipyridine, ethylenediamine, propylenediamine, N,N,N′-trimethylethylenediamine, ethylenediaminetetraacetic acid, alkyldiamines, other diamines, ethanolamine, triethanolamine, methylethanolamine, dimethylethanolamine, propanolamine, 3-butenylmagnesium, isobutylmagnesium bromide, cyclohexylmagnesium chloride, and amino acid.
- In an alternate embodiment at least one of Rs, and Rx are not positively charged cyclic amines, Cl or OH.
- In an alternate embodiment both Rs, and Rx are not positively charged cyclic amines, Cl or OH.
- In an alternate embodiment Rs, Rt and Rx are each not positively charged cyclic amines, Cl or OH.
- In a preferred embodiment Vinylbenzyl-Rx and Styrene-Rt are not divinylbenzene.
- In a preferred embodiment Rt is a hydrogen or a linear alkyl.
- In a preferred embodiment, the polymer will have a molecular weight between 1000 and 10,000,000 atomic units (A.U.) preferably between 10,000 and 1,000,000 A.U., most preferably between 25,000 and 250,000 A.U.
- In a preferred embodiment, the polymeric composition is in the form of a membrane. The membrane has a preferred thickness of 10-300 micrometers.
- In a preferred embodiment the membrane has an area specific resistance of 0.1 ohm-cm2 or less.
- It is understood that the process is not limited to the particular methodology, protocols and reagents described herein, as these can vary as persons familiar with the technology involved here will recognize. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only, and is not intended to limit the scope of the process. It also is to be noted that as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include the plural reference unless the context clearly dictates otherwise. Thus, for example, a reference to “a linker” is a reference to one or more linkers and equivalents thereof known to those skilled in the art. Similarly, the phrase “and/or” is used to indicate one or both stated cases can occur, for example, A and/or B includes (A and B) and (A or B).
- Unless defined otherwise, technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which the process pertains. The embodiments of the process and the various features and advantageous details thereof are explained more fully with reference to the non-limiting embodiments and/or illustrated in the accompanying drawings and detailed in the following description. It should be noted that the features illustrated in the drawings are not necessarily drawn to scale, and features of one embodiment can be employed with other embodiments as the skilled artisan would recognize, even if not explicitly stated herein.
- Any numerical value ranges recited herein include all values from the lower value to the upper value in increments of one unit, provided that there is a separation of at least two units between any lower value and any higher value. As an example, if it is stated that the concentration of a component or value of a process variable such as, for example, size, angle size, pressure, time and the like, is, for example, from 1 to 98, specifically from 20 to 80, more specifically from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, and the like, are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value are to be treated in a similar manner.
- Moreover, provided immediately below is a “Definitions” section, where certain terms related to the process are defined specifically. Particular methods, devices, and materials are described, although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the process.
- The term “polymer electrolyte membrane” as used here refers to both cation exchange membranes, which generally comprise polymers having multiple covalently attached negatively charged groups, and anion exchange membranes, which generally comprise polymers having multiple covalently attached positively charged groups. Typical cation exchange membranes include proton conducting membranes, such as the perfluorosulfonic acid polymer available under the trade designation NAFION from E. I. du Pont de Nemours and Company (DuPont) of Wilmington, Del.
- The term “anion exchange membrane electrolyzer” as used here refers to an electrolyzer with an anion-conducting polymer electrolyte membrane separating the anode from the cathode.
- The term “EMIM” as used here refers to 1-ethyl-3-methylimidazolium cations.
- The Term “CV” refers to cyclic voltammetry.
- The term “Millipore water” is water that is produced by a Millipore filtration system with a resistivity of at least 18.2 megaohm-cm.
- The term “imidazolium” as used here refers to a positively charged ligand containing an imidazole group. This includes a bare imidazole or a substituted imidazole. Ligands of the form:
- where R1-R5 are each independently selected from hydrogen, halides linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
- The term “pyridinium” as used here refers to a positively charged ligand containing a pyridine group. This includes a bare pyridine or a substituted pyridine. Ligands of the form:
- where R6-R11 are each independently selected from hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
- The term “phosphonium” as used here refers to a positively charged ligand containing phosphorous. This includes substituted phosphorous. Ligands of the form:
-
P+(R12R13R14R15) - where R12-R15 are each independently selected from hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
- The term “positively charged cyclic amine” as used here refers to a positively charged ligand containing a cyclic amine. This specifically includes imidazoliums, pyridiniums, pyrazoliums, pyrrolidiniums, pyrroliums, pyrimidiums, piperidiniums, indoliums, triaziniums, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
- The term “simple amine” as used here refers to a species of the form
-
N(R16R17R18), - wherein R16, R17 and R18 are each independently selected from hydrogen, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, but not polymers.
- The term “substituted ethene” as used here refers to a monomer of the form:
- wherein R1-R4 are each independently selected from hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, including polymers.
- The term “water purification system” as used here refers to a device that removes unwanted constituents from water and, in the case of a membrane-based device, one that employs a membrane as a barrier that allows certain substances to pass through while blocking others.
- The term “battery” as used here refers to a device that generates electricity via an electrochemical reaction between substances stored internally within the battery.
- The term “fuel cell” as used here refers to a device that generates electricity via an electrochemical reaction between substances that are supplied to the fuel cell from an external source.
- The term “electrolyzer” as used here refers to an electrochemical device that uses electrical energy to convert a substance into constituent substances. In the case of a water electrolyzer, the device uses electricity to convert water into hydrogen and oxygen.
- The term “CO2 capture system” as used here refers to a device that is able to separate CO2 from a gas or liquid stream.
- The examples provided here are merely illustrative and are not meant to be an exhaustive list of all possible embodiments, applications or modifications of the present electrochemical device. Thus, various modifications and variations of the described methods and systems of the invention will be apparent to those skilled in the art without departing from the scope of the invention. Although the invention has been described in connection with specific embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the chemical arts or in the relevant fields are intended to be within the scope of the appended claims.
- The objective of this example is to provide a number of alternate membranes that are useful for the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification.
- Generally, the synthesis procedure follows that in U.S. Pat. No. 9,370,773.
- Step 1: Inhibitor free styrene was prepared by washing styrene (Sigma Aldrich, Saint Louis, Mo.) with two equal volumes of 7.5% aqueous sodium hydroxide. The inhibitor free styrene was then washed with four equal volumes of water to make sure it was neutralized, and was then dried over anhydrous magnesium sulfate. The tert-butylcatechol (TBC) inhibitor in the vinylbenzyl chloride (VBC) was removed by extraction with 0.5% potassium hydroxide solution until a colorless extract was obtained. This extract was washed with water until neutral and then was dried over anhydrous magnesium sulfate.
- Step 2: Poly(vinylbenzyl chloride-co-styrene) was then synthesized by heating a solution of inhibitor free styrene (Sigma-Aldrich) (10.0581 g, 96.57 mmol) and vinylbenzyl chloride (Sigma-Aldrich) (6.2323 g, 40.84 mmol) in chlorobenzene (Sigma-Aldrich) (15 ml) at 60-65° C. in an oil bath for 12-18 hours under argon gas with AIBN (α,α′-Azoisobutyronitrile, Sigma-Aldrich) (0.1613 g, 0.99 wt % based on the total monomers weight) as initiator. The copolymer was precipitated in ethanol and dried under vacuum.
- Step 3: The resultant copolymer was dissolved in 1-Methoxy-2-propanol (Sigma Aldrich) to form a solution that was about 30% by weight of polymer.
- Step 4: The solution from step 3 was heated to 60° C., and 1-Decyl-2-methylimidazole was added and the solution was continuously stirred for 48 hours.
- Additional polymer solutions were prepared by replacing the 1-Decyl-2-methylimidazole with each of the following compounds: 1,1,3,3-Tetramethylguanidine, 1-Ethylpiperidine, 1-methylpyrrolidine, 2,2′-Bipyridyl, 2,3,5-Trimethylpyridine, 2-Methylpyridine, Pyridine, 3-Methylpyridine, 4,4′-dipyridyl, 4-Methylpyridine, N,N,N′,N′-Tetramethyl-1,6-hexanediamine, N,N-Dicyclohexylmethylamine, 1-(2-hydroxyethyl)imidazole, N,N-Dimethylcyclohexylamine, N-methyl Piperdine, Tetramethyl Imidazole, 1-methylimidazole, 1,2-dimethyl imidazole, Tributyl amine, triethyl amine, Trimethyl amine, Triphenyl phosphine, Tripropyl amine, 1,3-diaminopropane, Ethylenediamine, (Methylamino)ethanol, Triethanolamine, Ethanolamine, Ethylenediaminetetraacetic acid, Trimethylethylenediamine, 3-amino-1-propanol, Piperidine, 1,4′-Bipiperidine, 2,2,6,6-Tetramethylpiperidine, Pyrrolidine, 4,4′-dipyridyl, Triphenyl amine, 1,2-Dimethylindole, 1-Methylindole, Hexamethylenetetramine.
- Step 5: Next, an attempt was made to manufacture membranes from each of the solutions prepared in step 4 by casting them directly onto a polyethylene terephthalate (PET) liner. The thickness of the solution on the PET was controlled by a film applicator (MTI Corporation, Richmond, Calif.) with an adjustable doctor blade. The membranes were then dried in a vacuum oven at 80° C. for 300 minutes, and then 120° C. for 200 minutes.
- Membranes were successfully prepared from the following amines: 1,1,3,3-Tetramethylguanidine, 1-Decyl-2-methylimidazole, 1-Ethylpiperidine, 1-methylpyrrolidine, 2,2′-Bipyridyl, 2,3,5-Trimethylpyridine, 2-Methylpyridine, Pyridine, 3-Methylpyridine, 4,4′-dipyridyl, 4-Methylpyridine, N,N,N′,N′-Tetramethyl-1,6-hexanediamine, N,N-Dicyclohexylmethylamine, 1-(2-hydroxyethyl)imidazole, N,N-Dimethylcyclohexylamine, N-methyl Piperdine, Tetramethyl Imidazole, 1-methylimidazole, 1,2-dimethyl imidazole, Tributyl amine, triethyl amine, Trimethyl amine, Triphenyl phosphine, Tripropyl amine.
- The solutions made using 1,3-diaminopropane, Ethylenediamine, (Methylamino)ethanol, Triethanolamine, Ethanolamine, Ethylenediaminetetraacetic acid, Trimethylethylenediamine, 3-amino-1-propanol, Piperidine, 1,4′-Bipiperidine, 2,2,6,6-Tetramethylpiperidine, Pyrrolidine, 4,4′-dipyridyl, Triphenyl amine, 1,2-Dimethylindole, 1-Methylindole, Hexamethylenetetramine had too high of a viscosity to be cast with the MTI casting machine, but it is believed that they could have been cast using different equipment.
- Nuclear Magnetic Resonance (NMR) indicated that in each case between 20 and 40% of the vinylbenzyl chloride (VBC) was unreacted, so that the unreacted VBC represented between 5 and 30% of the total weight of the membrane.
- Measurements were performed where N,N-Dimethylformamide (DMF) was substituted for the Dowanol in Step 4. In those cases, the unreacted VBC was only about 1-3% of the weight of the polymer.
- The specific area resistance of the each of the membranes produced in Specific Example 1 was also measured. In all cases the resultant membranes had an area specific resistance below 0.1 ohm-cm2 in 1 M KOH so that they are useful as ion conductors for at least one of: the electrolysis of water, electrolysis of carbon dioxide, batteries, electric power generation using fuel cells, water purification, and CO2 capture systems.
- The objective of this example is to show that an anion-conducting membrane comprising a polymer comprising the reaction products of vinylbenzyl-Rs, vinylbenzyl-Rx and styrene-Rt, wherein
- (a) Rs is a positively charged amine or phosphine group,
- (b) Rx is independently selected from linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, and heteroalkylaryls,
- (c) Rt is independently selected from linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, and heteroalkylaryls,
- (d) Rx is a different chemical species than Rs,
also has properties that make the membrane useful for at least one of: the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification. - First a terpolymer comprising the reaction products styrene, vinylbenzyl chloride (VBC) and 4-(3-butenyl)styrene was synthesized.
- (a) Reacting VBC with a Grignard reagent 3-Butenylmagnesium bromide (Sigma Aldrich) in tetrahydrofuran (THF) to yield 4-(3-butenyl)styrene
- (b) Mixing 10 grams of styrene, 3 grams of 4-(3-butenyl)styrene, 1 gram of VBC and 0.14 g of AIBN in 20 grams of chlorobenzene, and polymerizing as in step 2 of Specific Example 1 above. The resultant polymer was functionalized with Tetramethyl Imidazole (TMIM) as described in steps 3 and 4 of Specific Example 1 above, and a membrane was prepared as described in step 5 of Specific Example 1. This provided a membrane comprising a copolymer comprising the reaction products of vinylbenzyl-Rs, vinylbenzyl-Rx and styrene-Rt where Rs=TMIM, Rx=a linear alkyl, and Rt=H.
- Polymers with Rx=Branched alkyl, a cyclic alkyl, a heteroalkyl, an aryl, an alkylaryl and a heteroalkylaryls can be synthesized in a similar manner by replacing Grignard reagent in step (a) in the previous paragraph with a Grignard reagent such as Isobutylmagnesium bromide (Sigma Aldrich), Cyclohexylmagnesium chloride (Sigma Aldrich), (1,3-Dioxan-2-ylethyl)magnesium bromide (Sigma Aldrich), 2-Methylbenzylmagnesium chloride (Sigma Aldrich), Benzylmagnesium chloride (Sigma Aldrich), 3-Methoxybenzylmagnesium chloride (Sigma Aldrich). Polymers with heteroaryls can be synthesized using the heteroaryl Grignard reagents disclosed in Barl, et al. (Heterocycles, Vol. 88, No. 2, 2014, pp. 827-844).
- In a similar manner, polymers where Rt is independently selected from linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, and heteroalkylaryls, can be manufactured by first creating a styrene-Rt by reacting VBC with one of the Grignard reagents discussed in the previous paragraph and then creating a membrane by substituting the styrene-Rt for styrene in steps 1 to 5 of Specific Example 1.
- The specific area resistance the membrane produced in Specific Example 2 was also measured. The membrane had an area specific resistance below 0.1 ohm-cm2 in 1 M KOH so that it may be useful for at least one of: the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification.
- The objective of this example is to show that an anion-conducting membrane comprising a polymer comprising the reaction products of vinylbenzyl-Rs, vinylbenzyl-Rx and styrene-Rt wherein
- (a) Rs is a positively charged amine or phosphine group,
- (b) Rx is Cl, OH, or a crosslink to other parts of the membrane,
- (c) Rt is hydrogen,
- (d) Rx is a different chemical species than Rs,
also has properties that make the membrane useful for at least one of: the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification. - First a PSTMIM membrane was created following the procedure in specific example 1.
- Next the membrane was soaked in 1 M KOH for 4 hours at room temperature. NMR as described in U.S. Pat. No. 9,943,841 shows that the resultant polymer contains benzyl-Rs groups, and benzyl-Rx groups, Rs=TMIM and Rx=OH. NMR also shows evidence of crosslinks through the benzyl group.
- The specific area resistance the membrane produced in Specific Example 3 was also measured. The membrane had an area specific resistance below 0.1 ohm-cm2 in 1 M KOH so that it may be useful for at least one of: the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification.
- The objective of this example is to provide additional examples of anion-conducting membranes comprising a polymer comprising the reaction products of vinylbenzyl-Rs, vinylbenzyl-Rx and styrene-Rt wherein
- (a) Rs is a positively charged amine or phosphine group,
- (b) Rx is an amine
- (c) Rt is hydrogen.
- (d) Rx is a different chemical species than Rs
also has properties that make the membrane useful for at least one of: the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification. - In an alternate synthesis the membrane of Specific Example 1 with Rs=tetramethylimidazole was soaked overnight in an aqueous solution of one of the following heteroalkyls or heteroalkylaryls. More specifically the membrane was submerged in an aqueous solution with 25 ml of water and 3.1 g of one of the following 1,1,3,3-tetramethylguanidine, N,N,N′-trimethylethylenediamine, ethylenediaminetetraacetic acid, ethanol amine, triethanol amine, hexamethylene tetramine, dimethyl indole and 2,2′-bipyridyl. Only dimethyl indole and 2,2′-bipyridyl failed to completely dissolve in water due to their lower solubility. This gave membranes where Rx groups are heteroalkyls and heteroalkylaryls.
- The specific area resistance of the each of the membranes produced in Specific Example 4 was also measured. In all cases the resultant membranes had an area specific resistance below 0.1 ohm-cm2 in 1 M KOH so that they are useful for at least one of: the electrolysis of water and carbon dioxide, batteries, electric power generation using fuel cells and water purification.
- While particular elements, embodiments and applications of the present invention have been shown and described, it will be understood that the invention is not limited thereto since modifications can be made by those skilled in the art without departing from the scope of the present disclosure, particularly in light of the foregoing teachings.
Claims (12)
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US14/704,935 US9370773B2 (en) | 2010-07-04 | 2015-05-05 | Ion-conducting membranes |
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